摘 要

3-蒈烯是自然界中极少数结构具有三元环的天然手型源化合物之一，在印度长叶松、欧洲赤松等松种中含量较高，是除α-蒎烯和β-蒎烯外产量第三高的松节油来源单萜烯。我国传统的松节油品种中3-蒈烯含量甚微，因此在我国没有足够的3-蒈烯资源储备，导致其研究成果也非常之少。然而，近年来在云南地区发现了一种特殊的思茅松（Pinus szemaoensis），其松节油中3-蒈烯含量最高可达38%，随着这些树种不断的进入采脂时期，3-蒈烯的资源正在快速增加，针对3-蒈烯的研究越来越受重视。

3-蒈烯的化学名称为3,7,7-三甲基双环[4.1.0]庚-3-烯，结构中同时具有六元环、三元环以及双键3个官能团，化学性质活泼，可以发生氧化、加成、异构、脱氢等多种化学反应，而氧化反应是对其进行改性的最有效方式之一。

本研究以自制的磷钼钨杂多酸为催化剂，H₂O₂为氧化剂，研究了3-蒈烯的环氧化反应，考察了溶剂类型、物料配比、反应温度及时间对结果的影响，得到3,4-环氧蒈烷的最佳制备工艺为：溶剂三氯甲烷、催化剂用量为3-蒈烯质量的2%，H₂O₂用量为3-蒈烯摩尔质量的1.2倍、反应温度35℃、反应时间6h，对应原料转化率92.96%，产物选择性92.05%。溶剂类型对于产物组成具有明显的影响，在除三氯甲烷外的其它大部分有机溶剂体系下，环氧化生成的3,4-环氧蒈烷会进一步开环生成3,4-蒈二醇。

另外，以CrO₃-Al₂O₃为催化剂，氧气为氧化剂，研究了3-蒈烯的烯丙位氧化反应。考察了催化剂用量、温度、时间以及氧气流量对氧化反应的影响，得到最佳氧化工艺为：CrO₃-Al₂O₃用量为3-蒈烯质量的3%、温度25℃、时间10h以及氧气流量25mL/min，对应原料转化率58.72%，α,β-不饱和酮类化合物总选择性86.07%（3-蒈烯-2-酮19.83%、2-蒈烯-4-酮4.61%、3-蒈烯-5-酮61.63%）。

关键词：3-蒈烯，环氧化，烯丙位氧化，3,4-环氧蒈烷，3-蒈烯-5-酮

Syntheses of oxygen-containing derivatives from 3-carene

ABSTRACT

3-Carene, mainly existing in some special pine trees, such as Pinus longifolia and Pinus sylvestris Linn, is one of the few chiral source compounds with ternary ring structure. It is ranked α-pinene and β-pinene after as the third largest production monoterpene from turpentine. Traditional turpentines produced in China were low in 3-carene, so it did not have adequate resources for further researches. As a result, its research results were very few. However, a special Pinus szemaoensis species has been found in yunnan in recent years, the content of 3-carene in turpentine from which was up to 38%. With these pine trees reached resin tapping period in succession, the resource of 3-carene was more and more abundant, and researches on it has received increasing attention.

The chemical name of 3-carene is 3,7,7- trimethylbicyclo [4.1.0] hept -3-ene,and there are a six-membered ring, a three-membered ring and a double bond in its molecular structure, so 3-carene is a compound with high reactivity. 3-carene could take various different kinds of reactions, including oxidation, addition, isomerization and dehydrogenation and so on, among which oxidation is one of the most effective ways for its modification.

In this paper, epoxidation of 3-carene was studied by using self-made phosphomolybdate tungsten heteropoly acid as catalyst and H2O2 as oxidant. The effects of solvent type, material ratio, reaction temperature and time on the reaction were investigated. The optimal preparation process of 3,4-epoxycarane was obtained as follows: trichloromethane as the solvent, the amount of catalyst was 2% of the mass of 3-carene, the amount of H2O2 was 1.2 times of the molar mass of 3-carene, reaction temperature was 35 oC and reaction time was 6 hours, the corresponding results of which were obtained as that conversion ratio of raw materials was 92.96% and the selectivity of product was 92.05%. Solvent type showed significant impact on the product composition. In most organic solvent systems except trichloromethane, 3,4-epoxycarane produced by epoxidation took place further ring-opening reaction and produced 3,4-carenediol.

In addition, allylic oxidation of 3-carene was made with CrO3-Al2O3 as catalyst and oxygen as oxidant. The effects of catalyst amount, temperature, time and oxygen flux on the oxidation were investigated. The optimum oxidation process was established as that catalyst amount was 3% of the mass of 3-carene, temperature was 25℃, time was 10 h and oxygen flux was 25 mL/min. Under the optimum process, the raw material conversion was 58.72%, and the total selectivity of α,β-unsaturated ketones was 86.07% (car-3-ene-2-one 19.83%, car-2-ene-4-one 4.61% and car-3-ene-5-one 61.63%).

Keywords: 3-carene, epoxidation, allylic oxidation, 3,4-epoxycarane, 3-carene-5-one

目录

第一章 前言 7

1.1 研究背景及意义 7

1.2国内外概况 8

1.2.1合成环氧蒈烷 8

1.2.2 合成蒈酮 9

1.2.3 合成蒈醇 9

1.3研究目标和内容 10

1.3.1研究目标 10

1.3.2研究内容 10

第二章 3-蒈烯环氧化实验 11

2.1实验过程 11

2.1.1试剂 11

2.1.2 设备 11

2.1.3催化剂制备 11

2.1.4 环氧化反应 11

2.1.5 产物分析 12

2.2结果与讨论 12

2.2.1产物构成 12

2.2.2结构鉴定 12

2.2.3溶剂类型选择 13

2.2.4 其他氧化工艺优化 14

2.3结论 16

第三章 3-蒈烯烯丙位氧化实验 17

3.1实验 17

3.1.1试剂 17

3.1.2设备 17

3.1.3催化剂制备及活化 17

3.1.4氧化反应 17

3.1.5 产物分析 18